Gas-phase solvolysis type reactions of SiCl3+ cations

Detalhes bibliográficos
Autor(a) principal: Firmino,Thiago Diamond Reis
Data de Publicação: 2010
Outros Autores: Menegon,Jair J., Riveros,José M.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Química Nova (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422010001000018
Resumo: Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.
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spelling Gas-phase solvolysis type reactions of SiCl3+ cationssilicylium ionsgas-phasesolvolysesGas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.Sociedade Brasileira de Química2010-01-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422010001000018Química Nova v.33 n.10 2010reponame:Química Nova (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0100-40422010001000018info:eu-repo/semantics/openAccessFirmino,Thiago Diamond ReisMenegon,Jair J.Riveros,José M.eng2010-12-16T00:00:00Zoai:scielo:S0100-40422010001000018Revistahttps://www.scielo.br/j/qn/ONGhttps://old.scielo.br/oai/scielo-oai.phpquimicanova@sbq.org.br1678-70640100-4042opendoar:2010-12-16T00:00Química Nova (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv Gas-phase solvolysis type reactions of SiCl3+ cations
title Gas-phase solvolysis type reactions of SiCl3+ cations
spellingShingle Gas-phase solvolysis type reactions of SiCl3+ cations
Firmino,Thiago Diamond Reis
silicylium ions
gas-phase
solvolyses
title_short Gas-phase solvolysis type reactions of SiCl3+ cations
title_full Gas-phase solvolysis type reactions of SiCl3+ cations
title_fullStr Gas-phase solvolysis type reactions of SiCl3+ cations
title_full_unstemmed Gas-phase solvolysis type reactions of SiCl3+ cations
title_sort Gas-phase solvolysis type reactions of SiCl3+ cations
author Firmino,Thiago Diamond Reis
author_facet Firmino,Thiago Diamond Reis
Menegon,Jair J.
Riveros,José M.
author_role author
author2 Menegon,Jair J.
Riveros,José M.
author2_role author
author
dc.contributor.author.fl_str_mv Firmino,Thiago Diamond Reis
Menegon,Jair J.
Riveros,José M.
dc.subject.por.fl_str_mv silicylium ions
gas-phase
solvolyses
topic silicylium ions
gas-phase
solvolyses
description Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.
publishDate 2010
dc.date.none.fl_str_mv 2010-01-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422010001000018
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422010001000018
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0100-40422010001000018
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv text/html
dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Química Nova v.33 n.10 2010
reponame:Química Nova (Online)
instname:Sociedade Brasileira de Química (SBQ)
instacron:SBQ
instname_str Sociedade Brasileira de Química (SBQ)
instacron_str SBQ
institution SBQ
reponame_str Química Nova (Online)
collection Química Nova (Online)
repository.name.fl_str_mv Química Nova (Online) - Sociedade Brasileira de Química (SBQ)
repository.mail.fl_str_mv quimicanova@sbq.org.br
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